JP2023176615A - Novel compounds, near-infrared-absorbing compositions, and optical filters - Google Patents

Abstract

To provide: compounds with high transmittance in a specific region of near-infrared (900 to 1200 nm) and excellent ability of cutting near-infrared of 700 to 750 nm; near-infrared-absorbing compositions with good dispersion stability and good light resistance; and optical filters.SOLUTION: The invention provides compounds represented by the general formula in the figure, where M represents a metal atom.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel compound, a near-infrared absorbing composition, and an optical filter.

Examples of near-infrared absorbing materials include near-infrared absorbing films that block heat rays, near-infrared absorbing plates, agricultural near-infrared absorbing films that selectively utilize sunlight, recording media that utilize near-infrared absorbed heat, and electronic devices. Used in a wide range of applications, including near-infrared cut filters for photography, near-infrared filters for photography, protective glasses, sunglasses, heat ray blocking films, dyes for optical recording, optical character reading and recording, for preventing copying of confidential documents, electrophotographic photoreceptors, and laser fusion. has been done.

Among them, solid-state image sensors (CCD image sensors, CMOS image sensors, etc.) in digital cameras, smartphones, etc. are sensitive to near-infrared rays, and when external light enters the light receiving part, it may be detected as noise. Sensitivity may be corrected by cutting off specific near-infrared rays with an optical filter.

In addition, in recent years, attempts have been made to add sensing functions (motion capture, spatial recognition, biometric authentication, etc.) using near-infrared rays to camera modules. For example, when using a near-infrared LED of 900 nm or 940 nm as the detection light, In some cases, the optical filter is required to be transparent to these detection wavelengths.

Thus, there is a need for a near-infrared absorbing material that selectively transmits visible light and some near-infrared rays, rather than uniformly cutting off near-infrared rays as in the past.

Known examples of near-infrared absorbing dyes include phthalocyanine dyes, cyanine dyes, diimonium dyes, squarylium dyes, croconium dyes, and indigo dyes. Among these, phthalocyanine dyes and cyanine dyes are particularly representative dyes. Each has distinct characteristics, and phthalocyanine dyes have a relatively robust structure, so they have good resistance to various types of dyes. Poor visibility and invisibility. On the other hand, cyanine dyes are generally used as dyes in a dissolved state, and therefore have very high transparency and invisibility, but have extremely poor various resistances, especially light resistance. Diimonium dyes, squarylium dyes, and croconium dyes also have characteristics similar to cyanine dyes.

As an indigo dye-based compound, Patent Document 1 discloses a boron compound. Further, Patent Document 2 discloses a palladium complex. However, these compounds have not been able to achieve both absorption in the near-infrared region and high heat resistance.

Japanese Patent Application Publication No. 2012-224593 JP2013-87233A

The object of the present invention is to provide a compound that has high transmittance in a specific region of near-infrared rays (900 nm to 1200 nm), excellent ability to cut near infrared rays in 700 nm to 750 nm, and good heat resistance. A further object of the present invention is to provide a near-infrared absorbing composition with good dispersion stability and light resistance, and an optical filter.

As a result of intensive research to solve the above-mentioned problems, the present inventors found that the compound represented by the general formula (1) has a high transmittance of near-infrared rays (900 nm to 1200 nm) in a specific region, and has a high transmittance of 700 nm. It was discovered that it has excellent ability to cut near infrared rays of up to 750 nm and good heat resistance, leading to the present invention.

That is, the present invention relates to a compound characterized by being represented by general formula (1).

General formula (1)

[In the formula, X ₁ to X ₁₂ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, and an aryl group that may have a substituent. Alkoxyl group, aryloxy group that may have a substituent, arylalkyl group that may have a substituent, cycloalkyl group that may have a substituent, Good alkylthio group, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom , nitro group, hydroxyl group, -SO ₃ H; -COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₁₂ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom. ]

Furthermore, the present invention relates to the above compound, wherein M is a divalent metal atom.

Further, the present invention relates to a near-infrared absorbing composition characterized by containing the above compound and a binder resin.

Further, the present invention provides that the near-infrared absorbing composition contains a metal component containing a metal atom selected from Li, Na, K, Cs, Ca, Fe, and Zr, and , the near-infrared absorbing composition, wherein the total amount of the metal atoms in the metal component is 1 to 1000 ppm by mass.

Further, the present invention relates to the above-mentioned near-infrared absorbing composition, wherein the water content in the near-infrared absorbing composition is 0.1 to 2.0% by mass based on the entire near-infrared absorbing composition.

Furthermore, the present invention relates to the near-infrared absorbing composition, which further contains a polymerizable compound and/or a photopolymerization initiator.

The present invention further relates to the near-infrared absorbing composition, characterized in that it further contains an organic dye having absorption in the wavelength range of 400 nm to 700 nm.

The present invention also relates to an optical filter characterized by having a coating formed from the near-infrared absorbing composition.

The present invention provides a compound that has high transmittance in a specific region of near-infrared rays (900 nm to 1200 nm), excellent ability to cut near infrared rays in 700 nm to 750 nm, and good heat resistance. Further, it is possible to provide a near-infrared absorbing composition with good dispersion stability and light resistance, and an optical filter.

FIG. 1 is an infrared absorption spectrum of compound (a) produced in Example 1. FIG. 2 is an infrared absorption spectrum of compound (b) produced in Example 2.

Define terms used herein. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". "C.I." mentioned herein means color index (C.I.). Colorants include pigments and dyes. The term "near infrared rays" mentioned herein means light with a wavelength of 700 nm to 2500 nm. Furthermore, the term "near-infrared absorbing dye" means a dye having one or more maximum absorptions in the wavelength range of 700 nm to 2,500 nm.

<Compound represented by general formula (1)>
The compound represented by general formula (1) of the present invention will be explained.

General formula (1)

[In the formula, X ₁ to X ₁₂ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, and an aryl group that may have a substituent. Alkoxyl group, aryloxy group that may have a substituent, arylalkyl group that may have a substituent, cycloalkyl group that may have a substituent, Good alkylthio group, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom , nitro group, hydroxyl group, -SO ₃ H; -COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₁₂ may be connected to form a 5-membered ring or a 6-membered ring together with the carbon atoms to which they are bonded.
M represents a metal atom. ]

The "alkyl group" of the alkyl group that may have a substituent is, for example, a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group. , n-octyl group, stearyl group, and 2-ethylhexyl group. "Alkyl group having a substituent" includes, for example, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoromethyl group, Propyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, Examples include 2,4-dichlorobenzyl group.

Examples of the "aryl group" of an aryl group that may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like.
"Aryl group having a substituent" includes, for example, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2- Aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, 2-amino Examples include anthraquinonyl group.

The "alkoxyl group" of the alkoxyl group which may have a substituent is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, Examples include straight chain or branched alkoxyl groups such as 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy.
"Substituted alkoxyl group" includes, for example, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2-ditrifluoropropoxy group, Examples include fluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, and benzyloxy group.

Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, and the "aryloxy group having a substituent" include, for example, p -methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, and the like.

Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, and an adamantyl group. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group and a 4-tert-butylcyclohexyl group.

The "alkylthio group" of the alkylthio group which may have a substituent is, for example, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc. can be mentioned.
Examples of the "alkylthio group having a substituent" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like.
Examples of "arylthio group having a substituent" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group, etc. .

The "alkylamino group" of the alkylamino group which may have a substituent is, for example, a methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, Octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert -pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1 -adamantamino group, 2-adamantamino group, etc.

The "arylamino group" of the arylamino group which may have a substituent is, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group. group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluorenamino group, 2-fluorenamino group, 2-thiazoleamino group, p-terphenylamino group, etc.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

Examples of acidic groups include -SO ₃ H and -COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Can be mentioned. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salts. Examples include quaternary alkyl ammonium salts of

Among the above substituents, preferred substituents for X ₁ to X ₁₂ include hydrogen atom, methyl group, methoxy group, fluorine atom, chlorine atom, bromine atom, and -SO ₃ H.

M represents a metal atom. Examples of metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, and Ti. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred.

(Synthesis method of compound represented by general formula (1))
A method for synthesizing the compound represented by general formula (1) will be described below. The compound represented by the general formula (1) can be obtained by reacting the compound represented by the general formula (2) with a metal salt in a solvent.

General formula (2)

[In the formula, X ₁₃ to X ₁₈ have the same meanings as X ₁ to X ₁₂ . ]

Examples of raw metal salts include acetates, acetylacetone complexes, metal halides, and the like.

The reaction temperature is not particularly limited, but is preferably in the range of 20 to 120°C, more preferably 50 to 120°C.

The reaction solvent is not particularly limited, but one in which the intermediate and metal salt can be dissolved is preferred. Specific examples include tetrahydrofuran, toluene, and N-methylpyrrolidone.

The amount of the metal salt used is 0.5 mol or more, preferably 0.7 to 2.0 mol, per 1 mol of the compound represented by general formula (2).

The reaction time is not particularly limited, but the progress of the reaction may be confirmed using a MALDI TOF-MS spectrum or a spectrophotometer to confirm the disappearance of the raw materials.

The compound represented by general formula (1) has absorption in a specific near-infrared region (700 nm to 750 nm) and has little absorption in the visible light region (400 nm to 550 nm), so it is used as a near-infrared absorbing dye. It has excellent functionality as a near-infrared absorber.

Examples of the compound represented by general formula (1) in the present invention include the following compounds, but the present invention is not limited thereto.

<Near-infrared absorbing dye>
The compound represented by general formula (1) of the present invention can be used as a near-infrared absorbing dye.

<Near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention is characterized by containing a compound represented by general formula (1) and a binder resin.

<Other near-infrared absorbing dyes>
The near-infrared absorbing composition of the present invention can contain other near-infrared absorbing dyes in addition to the compound represented by general formula (1). This allows the spectrum to be adjusted as appropriate. Other near-infrared absorbing pigments include, for example, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, indigo compounds (excluding compounds represented by general formula (1)), Examples include croconium compounds, azo compounds, quinoid complex compounds, dithiol metal complex compounds, and the like.

The content of the compound represented by the general formula (1) of the present invention is as follows: When other near-infrared absorbing dyes are used together as the near-infrared absorbing dyes, the content of the compound represented by the general formula (1) is as follows: The weight ratio of the compound represented by 1) is preferably in the range of 5/95 to 50/50.

<Organic dye with absorption between 400 nm and 700 nm>
The near-infrared absorbing composition of the present invention can contain an organic dye having absorption in the wavelength range of 400 nm to 700 nm. The compound represented by the general formula (1) contained in the near-infrared absorbing composition of the present invention has strong absorption in the wavelength range of 700 nm to 750 nm. By containing a dye, it can also be used as a near-infrared transmitting composition that blocks light of 400 nm to 750 nm and transmits light of 750 nm or more. Furthermore, by using other near-infrared absorbing dyes in combination, the compound represented by general formula (1) and other near-infrared absorbing dyes have near-infrared transmittance that transmits light with a longer wavelength than the absorption wavelength of the other dyes. It can also be used as a composition. In addition, by containing an organic dye that absorbs in a specific region of 400 nm to 700 nm in accordance with the wavelength of the light source for sensing, it can be used as a near-infrared absorbing composition that blocks unauthorized external light and improves sensing accuracy. can be used.

Examples of the organic dyes having absorption in the range of 400 nm to 700 nm include blue dyes, green dyes, yellow dyes, violet dyes, and red dyes.
Organic pigments may be used as the organic pigments, such as diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthrone, and indan. Anthraquinone pigments such as thoron, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, threne pigments, or Examples include metal complex pigments.
Furthermore, dyes may be used as the organic pigments, such as anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, triphenylmethane dyes, etc. Can be mentioned. When using dyes. An effective method is to use the polar groups of anionic dyes or cationic dyes to incorporate them into the resin and impart solubility in organic solvents.

(blue pigment)
Examples of blue pigments include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.

As a blue dye, C. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

Also, C. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc. are also included.

(green pigment)
Examples of green pigments include C.I. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58, C. I. Pigment Green 59, C. I. Pigment Green 62, C. I. Pigment Green 63 and the like.

As a green dye, C. I. Solvent Green 3, 20, 28, C. I. Acid Green 25, 27, 36, 37, 38, 41, 42, 44, C. I. Examples include bat greens 3, 6, and 8.

(yellow pigment)
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234, etc.

As a yellow dye, C. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 and the like.

Also, C. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. are also included.

(purple pigment)
As the purple pigment, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

As the purple dye, C. I. Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. can be mentioned.

Also, C. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97, etc. are also included.

(red pigment)
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 1 01, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 , 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208 , 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254 , 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296, etc. Can be mentioned.

Orange pigments that work similarly to red pigments include, for example, C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 73, and other orange pigments can be used.

As a red dye, C. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

Also, C. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, and the like.

Also, C. I. Also included are Solvent Red 52, 135, 146, 149, 168, 179, 207, and the like.

Although the above dyes have good spectral properties and excellent color development, they have problems with light resistance and heat resistance, and their properties may not be sufficient for use in optical filters.
Therefore, in order to improve these drawbacks, when the dye is in the form of a basic dye, it is preferable to form a salt using an organic acid or perchloric acid. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among these, naphthalene sulfonic acid such as Tobias' acid and perchloric acid are preferably used in terms of resistance.
Further, it is preferable to form a salt with a resin having an anionic group before use, and it is also preferable to use a salt formed with a resin having a betaine structure and an organic acid.
In addition, in the case of anionic dyes including acid dyes and direct dyes, it is recommended to use a compound with a cationic group or a resin with a cationic group as a salt-forming compound as a counter ion to improve heat resistance, light resistance, and solvent resistance. preferred in terms of gender.
Further, it is preferable to form a salt with a resin having a cationic group, and more preferably to form a salt with a resin having a cationic group in its side chain and an organic acid.
It is also preferable from the viewpoint of durability to convert the anionic dye into a sulfonamide and use it as a sulfonic acid amide compound.

<Dye derivative>
The near-infrared absorbing composition of the present invention can contain a dye derivative as necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, or phosphoric acid groups, as well as amine salts thereof, sulfonamide groups, or basic substituents such as tertiary amino groups at the terminals. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives include JP-A No. 2001-220520, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, JP 2017-156397 pamphlet, and phthalocyanine-based dye derivatives. Pigment derivatives are disclosed in JP-A No. 2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, and Patent No. 5753266. Anthraquinone-based pigment derivatives are described in JP-A-63-264674 and JP-A-09-09. -272812, JP 10-245501, JP 10-265697, JP 2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP 48-54128, JP-A-03-9961, JP-A 2000-273383, dioxazine dye derivatives, JP-A 2011-162662, thiazine indigo dye derivatives, JP-A 2007-314785, triazine dye derivatives are JP-A-61-246261, JP-A-11-199796, JP-A 2003-165922, JP-A 2003-168208, JP-A 2004-217842, and JP-A 2007-314681. , benzisoindole dye derivatives are disclosed in JP-A No. 2009-57478, and quinophthalone-based dye derivatives are described in JP-A Nos. 2003-167112, 2006-291194, 2008-31281, and 2012. -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic The substituent is described in JP-A No. 2004-307854, and the basic substituent is described in JP-A-2002-201377, JP-A 2003-171594, JP-A 2005-181383, and JP-A 2005-213404. Mention may be made of the dye derivatives described. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

These dye derivatives can be used alone or in combination of two or more.

The dye derivative is preferably added in an amount of 1 to 100% by weight, more preferably 3 to 70% by weight, and even more preferably 5 to 50% by weight, based on 100% by weight of the dye.

When the dye is a pigment, the dye derivative is adsorbed onto the pigment surface by adding a dye derivative and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling. , the primary particles of the pigment can be made finer than when no dye derivative is added.

By adding a pigment derivative to the pigment and performing a dispersion process such as wet dispersion using two rolls, three rolls, or beads, the pigment derivative is adsorbed to the pigment surface, and the pigment surface becomes polar and adsorbs the resin-type dispersant. is promoted, the compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and the dispersion stability and viscosity stability over time of the near-infrared absorbing composition are improved. In addition, due to improved compatibility, the near-infrared absorbing composition has excellent coating film stability over time when applied to a glass substrate, etc., and the waiting time from application of the near-infrared absorbing composition to exposure (PCD: The stability and characteristic dependence of pattern shape on Post Coating Delay (Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and line width sensitivity stability are improved. Furthermore, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress crystal precipitation due to aggregation and sublimation of the pigment when the coating film is heated and baked. Furthermore, variations in development time and development residues are also suppressed.

<Resin type dispersant>
The near-infrared absorbing composition of the present invention can contain a resin-type dispersant, if necessary. The resin-type dispersant has a pigment-affinity site that has the property of adsorbing to the pigment, and a relaxing site that has a high affinity for components other than the pigment and causes steric repulsion between dispersed particles. As the resin type dispersant, structurally controlled resins such as graft type (comb type) and block type are preferably used.

In terms of resin type, resin-type dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and polycarboxylic acids. Acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; poly(lower alkylene imine) and polyesters having free carboxyl groups. Amides and their salts formed by the reaction of Pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphoric acid esters, and the like.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, manufactured by BYK Chemie Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000 manufactured by Lubrizol Japan ,13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 3 8500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408 manufactured by BASF , 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. , Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine Techno.

The resin type dispersants can be used alone or in combination of two or more types.

The content of the resin type dispersant is preferably 0.1 to 200% by weight, more preferably 0.1 to 150% by weight based on 100% by weight of the dye. When used in an appropriate amount, good dispersibility can be obtained.

<Binder resin>
The near-infrared absorbing composition of the present invention contains a binder resin. The binder resin is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. Note that the transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, thermoplastic resin, thermosetting resin, active energy ray curable resin, and the like. Note that the active energy ray-curable resin may be a thermoplastic resin or a thermosetting resin that has an active energy ray-reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkaline development step when producing an optical filter, and an acidic group is required.

Binder resins can be used alone or in combination of two or more types.

The content of the binder resin is preferably 20 to 400% by mass, more preferably 50 to 250% by mass, based on 100% by mass of the dye. When contained in an appropriate amount, a film can be easily formed and good color properties can be easily obtained.

(Thermoplastic resin)
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of thermoplastic resins having alkali solubility include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of thermoplastic resins having alkali solubility include acrylic resins having acidic groups, α-olefin/(anhydrous) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydrous) maleic acid copolymer. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred from the viewpoint of improving developability, heat resistance, and transparency.

(Active energy ray-curable alkali-soluble resin)
The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. Ethylenically unsaturated double bonds can be introduced, for example, by methods (i) and (ii) shown below. The resin is three-dimensionally crosslinked due to the effect of active energy rays, thereby increasing crosslinking density and improving chemical resistance.

[Method (i)]
In method (i), for example, an ethylenically unsaturated monomer having an epoxy group is added to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer with another monomer. The carboxyl group of an unsaturated monobasic acid having a heavy bond is subjected to an addition reaction. Next, the generated hydroxyl group is reacted with a polybasic acid anhydride, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

Ethylenically unsaturated monomers having an epoxy group include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

Unsaturated monobasic acids include monobasic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Examples include carboxylic acids.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. In addition, if necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to reduce the remaining amount. It is also possible to hydrolyze the anhydride group.

Other monomers include the following. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate (meth)acrylates such as acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine, etc. Acrylamides, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate, or vinyl propionate. etc.

Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4- Phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl Acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. can be mentioned.

As a method similar to method (i), for example, a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer may be used. , is a method in which an ethylenically unsaturated monomer having an epoxy group is subjected to an addition reaction to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
Method (ii) involves adding an ethylenically unsaturated monomer having an isocyanate group to the side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer. This is a method in which the isocyanate groups of monomers are reacted.

The ethylenically unsaturated monomer having a hydroxyl group is, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, Examples include hydroxyalkyl methacrylates such as glycerol mono(meth)acrylate and cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester Also included are polyester mono(meth)acrylates to which 12-hydroxystearic acid and the like are added. From the viewpoint of suppressing coating film foreign matter, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferable, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Among them, glycerol mono(meth)acrylate is more preferable.

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate. It will be done.

Other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already explained, N-substituted maleimides, alkyleneoxy group-containing monomers, and phosphoric acid ester group-containing ethylenically unsaturated monomers. monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, Examples include N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, and the like. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO or propylene oxide (PO) modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, nonylphenol PO modified (meth)acrylate, and the like.

As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already described can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer. be.

(Alkali-soluble resin without ethylenically unsaturated double bonds)
The near-infrared absorbing composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bonds in order to adjust the degree of curing of the coating.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is preferably 4,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, in order to impart alkaline development solubility. Moreover, it is preferable that the value of Mw/Mn is 10 or less. If the weight average molecular weight (Mw) is less than 4,000, the adhesion to the substrate will decrease, making it difficult for the exposed pattern to remain. When it exceeds 100,000, the solubility in alkali development decreases, a residue is generated, and the linearity of the pattern deteriorates.
The acid value of the alkali-soluble resin in the present invention is 50 or more and 200 or less (KOHmg/g) in order to impart alkaline development solubility, preferably 20 to 300 or less, more preferably 90 or more and 170 or less. It is. If the acid value is less than 50, the solubility in alkaline development will decrease, a residue will be generated, and the linearity of the pattern will deteriorate. If the acid value is too high, the adhesion to the substrate will decrease, making it difficult for the exposed pattern to remain.

Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more.

(thermosetting compound)
In the present invention, it is preferable that the binder resin is used in combination with a thermoplastic resin and further contains a thermosetting compound. For example, when producing an optical filter using the near-infrared absorbing composition of the present invention, by including a thermosetting compound, it reacts during firing of the filter segment and increases the crosslinking density of the coating film, thereby making the filter segment heat resistant. The effect of suppressing the decrease in transmittance in the range of 480 nm to 650 nm, which is a region with high specific luminous efficiency, is achieved.

The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. It is not something that will be done. Epoxy compounds and oxetane compounds are preferably used in the near-infrared absorbing composition of the present invention.

Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted Polycondensates of dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), phenol and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and ketones. (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyl dimethanol) , α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) , polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

The content of the thermosetting compound is preferably 0.5 to 300% by mass, more preferably 1.0 to 50% by mass, based on 100% by mass of the near-infrared absorbing dye of the present invention. Appropriate heat resistance can be obtained when used in an appropriate amount.

The near-infrared absorbing composition can contain a curing agent and a curing accelerator to assist in curing the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Curing accelerators include, for example, amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (e.g., Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4 -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid adduct, etc.) Can be mentioned.

The content of the curing agent and curing accelerator is preferably 0.01 to 15% by mass, respectively, based on 100% by mass of the thermosetting compound.

<Polymerizable compound>
The near-infrared absorbing composition of the present invention can be made into a photosensitive near-infrared absorbing composition by containing a polymerizable compound and a photopolymerization initiator. Polymerizable compounds include monomers or oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins.

Examples of the polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxyethyl (meth)acrylate. Acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolation Various acrylic esters and methacrylic esters such as (meth)acrylic ester of melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples include trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

(Polymerizable compound having acid group)
The polymerizable compound can contain a polymerizable compound having an acid group. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups.

Polymerizable compounds having acid groups include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; polyhydric carboxylic acids and monohydroxyalkyl ( Examples include esterified products with meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Polymerizable compound with urethane bond)
The polymerizable compound can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting a (meth)acrylate having a hydroxyl group. Examples include polyfunctional urethane acrylates obtained by

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate , glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The polymerizable compounds can be used alone or in combination of two or more.

The blending amount of the polymerizable compound is preferably 1 to 50% by weight, more preferably 2 to 40% by weight based on 100% by weight of the nonvolatile content of the near-infrared absorbing composition. When blended in an appropriate amount, curability and developability are further improved.

<Photopolymerization initiator>
Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] -2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6- Triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O- oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime); Phosphine compounds such as (2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone Examples include borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds. Among these, oxime ester compounds are preferred.

The photopolymerization initiators can be used alone or in combination of two or more types.

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. When the pigment concentration of the near-infrared absorbing composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low, but oxime ester compounds are preferably used because they have high quantum efficiency. Ru.

Oxime ester compounds include oximes described in JP-A No. 2007-210991, JP-A 2009-179619, JP-A 2010-037223, JP-A 2010-215575, JP-A 2011-020998, etc. Examples include ester photopolymerization initiators.

The content of the photopolymerization initiator is preferably 2 to 200% by weight, more preferably 2 to 150% by weight, based on 100% by weight of the dye. When incorporated in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
Furthermore, the near-infrared absorbing composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives , naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy esters , acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'- Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the above-mentioned sensitizers, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are mentioned as sensitizers that can particularly suitably sensitize. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis (dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole and the like are used.

More specifically, there are "Pigment Handbook" (edited by Makoto Okawara et al., 1986, Kodansha), "Chemistry of Functional Pigments" (edited by Makoto Okawara et al., 1981, CMC), "Dye Handbook" (edited by Shin Okawara et al., 1981, CMC), and " Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (CMC, 1986). In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may also be included.

The sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60% by weight, more preferably 5 to 50% by weight based on 100% by weight of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol-based chain transfer agent>
The near-infrared absorbing composition of the present invention preferably contains a thiol chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, thiyl radicals that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen are generated in the radical polymerization process after light irradiation, so the resulting near-infrared absorbing composition has a high Sensitivity.

Further, polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene and ethylene groups are preferred. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the base material.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid Tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s- Examples include triazines, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.1 to 20% by weight, more preferably 0.1 to 10% by weight based on 100% by weight of nonvolatile content of the near-infrared absorbing composition. When contained in an appropriate amount, photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The near-infrared absorbing composition of the present invention can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during exposure using photolithography, making it easier to obtain a pattern with a desired shape.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, and 2-ethylcatechol. Propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4- Alkylcatechol compounds such as tert-butylcatechol and 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propyl Alkylresorcinol compounds such as resorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, Alkylhydroquinone compounds such as 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the near-infrared absorbing composition. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

<Ultraviolet absorber>
The near-infrared absorbing composition of the invention may also contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. .

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total of 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the near-infrared absorbing composition. When contained in an appropriate amount, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy- 5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethyl ethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-( Reaction product of 2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1 , 3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro- Examples include 2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer type and polymer type compounds having a benzotriazole structure can also be used.

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6 -bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) )-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 2,4-bis(2-hydroxy-4- butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyl oxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris Examples include (2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomer type and polymer type compounds having a triazine structure can also be used.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2 , 2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like. Other oligomer type and polymer type compounds having a benzophenone structure can also be used.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. Other oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

<Antioxidant>
The near-infrared absorbing composition of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiator and thermosetting compounds contained in the near-infrared absorbing composition from oxidizing and yellowing due to heat curing or the thermal process during ITO annealing, and reduce the transmittance of the coating film. can be improved. In particular, when the concentration of the colorant in the coloring composition is high, the amount of crosslinking component in the coating film decreases, and measures such as using a highly sensitive crosslinking component and increasing the amount of photopolymerization initiator are taken, resulting in stronger yellowing during the heat process. can be seen. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and obtain a high transmittance of the coating film.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

Antioxidants can be used alone or in combination of two or more.

In addition, the content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the solid content of the near-infrared absorbing composition because transmittance, spectral characteristics, and sensitivity are good. .

<Amine compounds>
The near-infrared absorbing composition can contain an amine compound to reduce dissolved oxygen.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, Examples include 2-ethylhexyl 4-dimethylaminobenzoate and N,N-dimethylpara-toluidine.

<Leveling agent>
The near-infrared absorbing composition can contain a leveling agent to improve the leveling properties of the composition during coating. The leveling agent is preferably dimethylsiloxane having a polyether structure or polyester structure in its main chain, for example. Examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Industries and BYK-333 manufactured by BYK Chemie Company. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in its main chain and dimethylsiloxane having a polyester structure in its main chain can be used together. The content of the leveling agent is preferably 0.003 to 0.5% by weight based on 100% by weight of the nonvolatile content of the near-infrared absorbing composition.

The leveling agent is, for example, a type of so-called surfactant that has a hydrophobic group and a hydrophilic group in its molecule, and is a compound that has a hydrophilic group but has low solubility in water and can lower surface tension. Dimethylpolysiloxane having polyalkylene oxide units can be preferably used as the leveling agent. Polyalkylene oxide units include, for example, polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

In addition, the bonding forms of polyalkylene oxide units with dimethylpolysiloxane are pendant type, in which polyalkylene oxide units are bonded to repeating units of dimethylpolysiloxane, terminal modified type, in which polyalkylene oxide units are bonded to the terminals of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any linear block copolymer type in which the polymers are alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray, and include, for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ- 2207 is mentioned.

Anionic, cationic, nonionic, or amphoteric surfactants can also be added to the leveling agent as an auxiliary agent. Two or more surfactants may be used in combination.

Examples of the anionic surfactant added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, and alkyldiphenyl ether disulfone. Sodium lauryl sulfate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include acid esters.

Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Examples of nonionic surfactants to be added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearer. amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<Storage stabilizer>
The near-infrared absorbing composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chloride such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include organic phosphines and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on 100% by weight of the dye.

<Adhesion improver>
The near-infrared absorbing composition of the present invention can contain an adhesion improver such as a silane coupling agent in order to improve the adhesion to the base material. By improving the adhesion by the adhesion improver, the reproducibility of fine lines becomes better and the resolution improves.

Examples of adhesion improvers include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane. (Meth)acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy Silane, mercapto compounds such as 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, and sulfides such as bis(triethoxysilylpropyl)tetrasulfide. , and silane coupling agents such as isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on 100% by weight of the colorant in the near-infrared absorbing composition. It is more preferable within this range because the effect is large and the balance between adhesion, resolution, and sensitivity is good.

<Organic solvent>
The near-infrared absorbing composition can contain an organic solvent. This facilitates adjustment of the viscosity of the composition.

Examples of organic solvents include ethyl lactate, butyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate , 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m -xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol mono Isopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether , ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, Cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene Glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, and the like.

Among the above-mentioned organic solvents, in the case of coating applications, it is preferable to include an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Method for producing near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention is prepared by adding a dye to a dye carrier such as a dispersant, a binder resin, and/or an organic solvent, preferably together with a dispersion aid (a dye derivative or a surfactant), using a kneader, It can be produced by finely dispersing it using various dispersion means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (dye dispersion). At this time, two or more types of dyes may be simultaneously dispersed in the dye carrier, or they may be separately dispersed in the dye carrier and mixed. If the pigment, such as a dye, has high solubility, specifically, if it is highly soluble in the organic solvent used, dissolved by stirring, and no foreign matter is detected, it is manufactured by finely dispersing it as described above. There's no need.

When used as a photosensitive near-infrared absorbing composition (resist material), it can be prepared as a solvent-developable or alkali-developable near-infrared absorbent composition. The solvent-developable or alkaline-developable near-infrared absorptive composition comprises the dye dispersion, a polymerizable compound and/or a photopolymerization initiator, and, if necessary, a solvent, other dispersion aids, additives, etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the near-infrared absorbing composition, or may be added later to the prepared near-infrared absorbing composition.

<Removal of coarse particles>
The near-infrared absorbing composition of the present invention can be produced into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, etc. It is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As described above, it is preferable that the near-infrared absorbing composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Moisture content in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention preferably has a water content of 0.1 to 2.0% by mass based on the entire near-infrared absorbing composition.

When the water content is within the above range, the near-infrared absorbing composition has excellent dispersion stability and sensitivity even after being stored over time.

The content of water is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, based on the total amount of the near-infrared absorbing composition. If the water content is sufficiently small within this range, problems with the dispersion stability and sensitivity of the near-infrared absorbing composition are unlikely to occur even after storage over time.

The method for controlling the water content is not particularly limited, and any known method can be used. Examples include a method of producing a near-infrared absorbing composition while blowing dry inert gas, and a method of adding molecular sieves to dehydrate the composition after production. Among these, a method of manufacturing while blowing dry inert gas is preferred.

The water content can be measured by a known method such as the Karl Fischer method.

<Specific metal atomic weight in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention contains small amounts of Li, Na, K, Cs, Ca, Fe, and Zr (hereinafter, specific metal atoms) in addition to the compound represented by general formula (1) and the constituent components of the organic dye. There may be metal components including The presence of a large amount of metal components containing these specific metal atoms may impair storage stability, reduce heat resistance, or cause a decrease in sensitivity when prepared in the form of a photosensitive near-infrared absorbing composition. be.
Furthermore, optical filters made using near-infrared absorptive compositions containing a large amount of metal components containing specific metal atoms may generate foreign matter, which tends to cause a decrease in transmittance. The total content of specific metal atoms in the metal components contained in the near-infrared absorbing composition of the present invention is preferably 1 to 1000 ppm by mass based on the entire near-infrared absorbing composition.

The total amount of specific metal atoms contained in the near-infrared absorbing composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, based on the entire near-infrared absorbing composition. Further, the lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 ppm or more by mass, more preferably 5 ppm or more by mass, based on the entire near-infrared absorbing composition. Within the above range, it is possible to obtain a near-infrared absorbing composition that can reduce costs, have excellent storage stability, and form an optical filter with little generation of foreign matter or decrease in transmittance.

The content of each specific metal atom contained in the near-infrared absorbing composition of the present invention is preferably 100 mass ppm or less, and 50 mass ppm or less, based on the entire near-infrared absorbing composition. is more preferable.

In addition, when the metal atom M in the compound represented by general formula (1) or a part of the organic dye structure contains metal atoms such as Ni, Zn, Pt, Mn, and Co, the compound or the organic These metal atoms may be present that do not form part of the dye structure. It is better to have fewer such metal atoms, and they can be removed in the same way as specific metal atoms by the following method. Furthermore, it is also preferable that materials such as Cs, Ti, Si, and Pd, which are mixed in by materials (eg, catalysts) used in the manufacturing process of various raw materials for near-infrared absorbing compositions, are at a low concentration.

Methods for removing metal atoms mixed in from various raw materials contained in near-infrared absorbing compositions or equipment during the manufacturing process include JP 2010-83997, JP 2018-36521, and JP 7-198928. Examples include the method of washing with water as described in Japanese Patent Application Laid-Open No. 8-333521, JP-A No. 2009-7432, etc., and the method of removing magnetic foreign matter using a magnet described in JP-A No. 2011-48736. Use methods accordingly.

The content of specific metal atoms can be measured by inductively coupled plasma emission spectroscopy (ICP).

<Amount of toluene in near-infrared absorbing composition>
The near-infrared absorbing composition of the present invention may contain toluene, and when it contains toluene, the content of toluene is preferably 0.1 to 10 ppm by mass. The upper limit of the content of toluene is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and even more preferably 0.4 mass ppm or more.

<Application>
The near-infrared absorbing composition of the present invention can be used, for example, in the following applications.

(optical filter)
The optical filter of the present invention is characterized by having a coating formed of the near-infrared absorbing composition of the present invention. The optical filter of the present invention includes a near-infrared cut filter and a near-infrared transmission filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye, and has the role of blocking near-infrared rays and transmitting visible light. On the other hand, near-infrared transmitting filters are composed of pigments that absorb visible light in addition to near-infrared absorbing pigments, and block visible light and near-infrared rays in the wavelength range that the near-infrared absorbing pigments absorb, and furthermore, It has the role of transmitting near-infrared wavelengths.

[Near infrared cut filter]
Near-infrared cut filters are used, for example, in the following applications.

<<Digital camera>>
Digital cameras recognize colors by separating the light they receive when taking an image using red, green, and blue filters and sending it to a photodiode that converts the light into electrical signals. However, since photodiodes also react to near-infrared rays and convert them into electrical signals, a near-infrared cut filter can be used to block this. It is important that a filter that blocks near-infrared rays has little absorption in the visible region. If there is a lot of absorption in the visible region, the received light will be colored, which will have an adverse effect on the photodiode's color recognition. Since the compound of the present invention has low absorption in the visible region and is highly invisible, it has little adverse effect on color recognition by a photodiode.

<<Biometric sensor>>
Smartphones, tablet computers, bank ATMs, multimedia terminals, etc. are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication for security purposes. In particular, the development of fingerprint authentication technology used in smartphones and tablet computers has been rapid.As photodiodes have changed from inorganic to organic photodiodes, the scope of authentication has increased to screen size (full screen), and organic EL displays, liquid crystal displays, etc. An in-display fingerprint authentication sensor has been developed.

However, many of the built-in display fingerprint sensors use an optical method that illuminates the fingerprint with various light sources installed inside the display and senses the reflected light. If strong light with a wide range of wavelengths is incident on the sensor, there is a problem that it will cause noise during image capture, so there are some concerns about accuracy when using it outdoors.For bank ATMs and multimedia terminals. The same is true for hand vein authentication, and stores with strong lighting or sunlight are taking measures such as covering the store with a cover to block external light.

Near-infrared cut filters are effective in solving these problems by absorbing and preventing unauthorized external light from entering the sensor.

For example, when setting it on the front panel of a smartphone or tablet computer, it is necessary to have a good design, but the compound of the present invention has the advantage of being suitable for use because it does not absorb in the visible region and is invisible, that is, it is highly transparent. . Further, since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can be preferably used in the process of manufacturing a sensor, or a touch sensor or touch panel incorporating the sensor.

In addition, external light that becomes noise in biometric authentication applications is light in the range of 650 nm to 1000 nm that passes through living organisms.In particular, light in the range of 650 nm to 800 nm is abundant in living spaces, so it is difficult to cut light in this wavelength range. Further improve the accuracy of biometric authentication. By combining a blue or green pigment that absorbs from 650 nm to 700 nm with a near-infrared absorbing pigment, the accuracy of biometric authentication can be further improved, although invisibility is reduced.

The blue pigment is, for example, C.I. I. Pigment Blue 15:6, C. I. Pigment Blue 15:3, C. I. Pigment Blue 15:1 and the like. The green pigment is, for example, C.I. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58, C. I. Pigment Green 59, C. I. Pigment Green 62, C. I. Pigment Green 63 and the like.

<<Display>>
Near-infrared cut filters can also be incorporated into displays. Specifically, a liquid crystal display with a touch panel function such as an electronic whiteboard can be mentioned. This liquid crystal display with a touch panel function has three functions: display, writing, and storage, and the built-in touch panel also uses optical methods such as infrared scanning method and infrared projection method. The problem was the noise caused by the external light mentioned above. Since liquid crystal displays with a touch panel function are often used in schools and the like, accuracy and responsiveness to touch are important. By incorporating the optical filter of the present invention into a display, it is possible to cut out external light that causes noise, which is preferable.
Furthermore, the optical filter of the present invention can be preferably used as an antireflection film for various displays using liquid crystals, organic EL, Mini-LED, and Micro-LED. By suppressing the reflection of not only visible light but also light in the near-infrared region, there is an advantage that the black display on the display can be made darker. Since the near-infrared absorbing composition of the present invention has excellent heat resistance, it can also be preferably used for resistance to steps required in display manufacturing.

[Near infrared transmission filter]
LEDs with wavelengths such as 850 nm, 900 nm, and 940 nm have become widespread, and are used for distance measurement in autonomous driving, biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or a combination thereof), and light detection in various sensors. used in However, since light rays of all wavelengths exist in the atmosphere, such as ultraviolet rays, visible light, and near-infrared rays, a filter is required to block light of wavelengths other than those to be detected. By combining a near-infrared absorbing dye with a dye that absorbs visible light, an ultraviolet absorber, etc., it is possible to transmit only light with a wavelength longer than the absorption wavelength of the near-infrared absorbing dye, while blocking light with a shorter wavelength. can. Specifically, it is preferable to combine the compound of the present invention with a blue dye, a yellow dye, a red dye, or a purple dye. For coating purposes, the blue pigment is C. I. Pigment Blue 15:3 or C.I. I. Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 139, red pigment is C.I. I. Pigment Red 254, C. I. Acid Red 52 or C. I. Acid Red 289, purple pigment is C. I. It is preferable to use Pigment Violet 23. In addition, for molding applications, the blue pigment is C. I. Pigment Blue 15:3 or C.I. I. Pigment Blue 15:6, yellow pigment is C.I. I. Pigment Yellow 147, red pigment is C.I. I. Solvent Red 52 is preferred.

[Optical filter manufacturing method]
The optical filter of the present invention can be manufactured by a printing method or a photolithography method. Formation of filter segments by printing can be patterned by printing and drying a near-infrared absorbing composition, so the filter manufacturing method is low cost and excellent in mass productivity. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. It is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted using dispersants and extender pigments.

When forming filter segments by photolithography, a near-infrared absorbing composition prepared as a solvent-developed or alkali-developed resist material is applied onto the substrate by spray coating, spin coating, slit coating, roll coating, etc. Depending on the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with the film or in a non-contact state. Thereafter, the uncured portion is removed by immersion in a solvent or alkaline developer or sprayed with a developer to form a desired pattern, and the same operation is repeated for other colors to produce a filter. I can do it. Furthermore, in order to promote polymerization of the resist material, heating can be applied as necessary. According to the photolithography method, a filter with higher precision can be manufactured than the above-mentioned printing method.

Although the substrate is not particularly limited, a sheet-like, film-like, or plate-like transparent base material can be used. The color may be colorless or colored, but is not particularly limited. The material of the transparent base material is a highly transparent material, for example, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or triacetyl cellulose (TAC). Examples include acrylic resins such as methyl methacrylate copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylimide resins, and glass plates.

For development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine may also be used. Moreover, an antifoaming agent and a surfactant can also be added to the developer. In order to increase the ultraviolet exposure sensitivity, after coating and drying the above resist material, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, was coated and dried to form a film that prevents polymerization inhibition due to oxygen. After that, exposure to ultraviolet light can also be performed.

The optical filter of the present invention can be manufactured by an electrodeposition method, a transfer method, an inkjet method, etc. in addition to the above-mentioned method.

(molding application)
The near-infrared absorbing composition of the present invention can also be used for molding purposes. Note that the term "molding application" refers to an application for producing a film or a three-dimensional body by a method other than coating.
When the near-infrared absorbing composition is used for molding purposes, it is preferably a melt-kneaded product of the compound of the present invention and a thermoplastic resin.

[Thermoplastic resin]
Examples of thermoplastic resins included in the near-infrared absorbing composition for molding include polyolefin resins, acrylic resins, polystyrene resins, polyester resins, polyamide resins, polycarbonate resins, cycloolefin resins, and polyetherimide resins.

<<Polyamide resin>>
Polyamide resin is a crystalline resin, and can be synthesized, for example, by subjecting a carboxylic acid component to a dehydration condensation reaction with a compound (Am) having two or more amino groups.

Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, and terephthalic acid. Note that, as the carboxylic acid component, a compound having three or more carboxyl groups can be used.
As the compound (Am) having two or more amino groups, known compounds can be used, for example, ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, triethylene Aliphatic polyamines such as tetramine; isophorone diamine, dicyclohexylmethane-4,4'
- Aliphatic polyamines including alicyclic polyamines such as diamine; aromatic polyamines such as phenylene diamine and xylylene diamine; 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino- 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, 3-(2-hydroxypropyl)- Examples include diamino alcohols such as o-xylene-α,α'-diamine.
Examples of commercially available polyamide resins include nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), nylon 610, and the like.

<<Polycarbonate resin>>
Polycarbonate resin is an amorphous resin, and is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or diester carbonate. In the case of a synthetic reaction using phosgene, for example, an interfacial method is preferred. Furthermore, in the case of a synthetic reaction using a carbonic acid diester, a transesterification method in which the reaction is carried out in a molten state is preferred.

Aromatic dihydroxy compounds include, for example, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2 , 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3, Bis(hydroxyaryl)alkanes such as 5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1, Bis(hydroxyaryl)cycloalkanes such as 1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiarylethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4 , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 Examples include dihydroxydiarylsulfoxides such as '-dimethyldiphenylsulfoxide, dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. Further, piperazine, dipiperidylhydroquinone, resorcinol, and 4,4'-dihydroxydiphenyls may be used in combination.

Examples of the carbonate precursor include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, more preferably 16,000 to 27,000. Note that the viscosity average molecular weight in this specification is a value calculated from the solution viscosity measured at a temperature of 25° C. using methylene chloride as a solvent.

Commercially available polycarbonate resins include, for example, Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 23,000), and Iupilon E-2000. (manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 27,000).

<<Cycloolefin resin>>
Cycloolefin resin is an amorphous resin having an alicyclic structure in its main chain and/or side chain. Examples of the types of alicyclic structures include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. Among these, norbornene polymers are preferred because they have excellent moldability and transparency. Norbornene monomers include, for example, bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.12,5]deca-3,7-diene ( Common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]dec-3-ene (common name: methanotetrahydrofluorene), Tetracyclo[4.4.0.12, 5.17,10] dodec-3-ene (common name: tetracyclododecene) and the like.
Examples of commercially available cycloolefin resins include Topas (manufactured by Polyplastics) and Appel (manufactured by Mitsui Chemicals).

<<Polyetherimide resin>>
Polyetherimide resin is an amorphous resin with a glass transition temperature of over 180°C, and has good transparency, high strength, high heat resistance, high elastic modulus, and wide chemical resistance. Therefore, they are widely used in a variety of applications such as automotive, telecommunications, aerospace, electrical/electronic, transportation, and healthcare.
One process for producing polyetherimide resins is by polymerization of an alkali metal salt of a dihydroxy aromatic compound, such as bisphenol A disodium salt (BPA.Na2), and bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be controlled in two ways. The first method is to use a molar excess of bis(halophthalimide) relative to the alkali metal salt of the dihydroxyaromatic compound. The second method is to prepare bis(halophthalic anhydride) in the presence of a monofunctional compound such as phthalic anhydride, which forms an end-capping agent. Phthalic anhydride reacts with some organic diamines to form monohalobis(phthalimide). Monohalo-bis(phthalimide) acts as an end-capping agent in the polymerization step by reaction with phenoxide end groups on the growing polymer chain.
Commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industries Corporation).

The thermoplastic resin is preferably a crystalline resin with a melting point of 100 to 500°C or an amorphous resin with a glass transition temperature of 60 to 300°C. Note that both the melting point and the glass transition temperature can be measured using a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

The near-infrared absorbing composition for molding can contain additives in addition to the compound of the present invention and the thermoplastic resin. Examples of additives include ultraviolet absorbers, light stabilizers, antioxidants, colorants, and dispersants. These additives are compounds known for molded body applications.

Ultraviolet absorbers are used to impart ultraviolet resistance to molded products. Examples of the ultraviolet absorber include benzophenone, benzotriazole, triazine, and salicylic acid esters. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

The light stabilizer is used to impart UV resistance to the molded article, and is preferably used in combination with a UV absorber. The light stabilizer is preferably a hindered amine light stabilizer, for example. The content of the light stabilizer is preferably 0.01 to 5% by weight based on 100% by weight of the composition.

Antioxidants are used to reduce deterioration of molded articles when exposed to natural light or artificial light sources and exposed to high temperatures. Preferably, the antioxidant is, for example, a monophenol type, a bisphenol type, a polymer type phenol type, a sulfur type, a phosphoric acid type, or the like. The content of the antioxidant is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

The dispersant is used to more uniformly disperse the near-infrared absorbing pigment in the molded article. Preferred examples of the dispersant include polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, and saponified fatty acid wax. The content of the dispersant is preferably 50 to 250% by weight based on 100% by weight of the near-infrared absorbing dye.

[Preparation of near-infrared absorbing composition for molding]
The near-infrared absorbing composition for molding can be produced by melt-kneading the compound of the present invention and a thermoplastic resin. The melting and kneading temperature varies depending on the resin, but is preferably 230°C or higher, more preferably 270°C or higher. Note that it is preferable to cool the mixture after melting and kneading. The upper limit of the melt-kneading temperature is not limited because it varies depending on the type of thermoplastic resin. The upper limit is preferably 500°C or less, more preferably 450°C or less. Further, the above upper limit needs to be lower than the sublimation temperature or lower than the decomposition temperature of the compound of the present invention.

Examples of the melt-kneading device include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder.

The resin composition is preferably produced as a so-called masterbatch. When a masterbatch is prepared and then melt-kneaded with a diluted resin (thermoplastic resin) to produce a molded object, the compound of the present invention is contained in the molded object compared to a molded object prepared without using a masterbatch. It is easy to disperse uniformly and can suppress aggregation of the compound. This improves the transparency of the molded body. In producing the masterbatch, it is preferable to mold the masterbatch into pellets using a pelletizer after the melting and kneading.
When produced as a masterbatch, the content of the near-infrared absorbing dye is preferably 0.01 to 20% by weight, more preferably 0.05 to 2% by weight based on 100% by weight of the composition.

(optical recording medium)
The near-infrared absorbing composition of the present invention can be used as an optical recording medium. When a coating or molded article formed from a near-infrared absorbing composition is irradiated with near-infrared rays, the crystal state of the compound of the present invention changes, and the refractive index of the coating or molded article changes. This principle is used in recording media such as optical discs.

(Laser welding material/laser marking material)
The near-infrared absorbing composition of the present invention can be used as a laser welding material or a laser marking material. When a coating or a molded article formed from a near-infrared absorbing composition is irradiated with a laser having a wavelength that is absorbed by the compound of the present invention, the compound absorbs the laser light and generates heat, thereby melting and carbonizing the resin. When melted, it can be welded to other resins, making marking possible.

The present invention will be described below based on examples, but the present invention is not limited thereto. In addition, in Examples and Comparative Examples, "parts" means "parts by mass." Moreover, "PGMAc" means propylene glycol monomethyl ether acetate.

(Compound identification method)
Infrared absorption spectra and MALDI TOF-MS spectra were used to identify the compounds used in the present invention. MALDI TOF-MS spectra were performed using a MALDI mass spectrometer autoflex III manufactured by Bruker Daltonics, and the obtained compound was determined by matching the molecular ion peak of the obtained positive mode mass spectrum with the mass number obtained by calculation. Identified. The infrared absorption spectrum was measured by the ATR method using Nicolet is5 FT/IR-410 manufactured by Thermo Fisher Scientific Co., Ltd. at a resolution of 2 cm −1 .

(Method for measuring water content of near-infrared absorbing composition)
The water content (mg) was measured using a Karl Fischer titrator (volume titration type water measuring device KF-06 model manufactured by Mitsubishi Chemical Corporation), and the water content (%) was calculated using the following formula.
Moisture content (%) = [moisture content (mg) / measurement sample amount (mg)] x 100

(Method for measuring specific metal atoms in near-infrared absorbing composition)
The amount of specific metal atoms in the near-infrared absorbing composition is determined by decomposing the powder of the near-infrared absorbing composition dried at 180°C using microwaves, and then using an ICP emission spectrometer Varian 720-ES manufactured by Agilent Technologies. did.

(Acid value of resin type dispersant and binder resin)
The acid values of the resin-type dispersant and binder resin were determined by potentiometric titration using a 0.1N potassium hydroxide/ethanol solution. The acid value of the resin-type dispersant and binder resin indicates the acid value of nonvolatile components.

(Weight average molecular weight (Mw) of acidic resin type dispersant and binder resin)
The weight average molecular weight (Mw) of the acidic resin-type dispersant and binder resin was measured using TSK gel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent. It is the weight average molecular weight (Mw) measured using polystyrene.

(Weight average molecular weight (Mw) of basic resin type dispersant)
The weight average molecular weight (Mw) of the basic resin type dispersant was measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC equipped with an RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) with 3mM triethylamine and 10mM LiBr as the developing solvent. This is the weight average molecular weight (Mw) in terms of polystyrene, measured using an N,N-dimethylformamide solution.

(Amine value of resin type dispersant)
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted into the equivalent amount of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of nonvolatile components.

(Quaternary ammonium salt value of resin type dispersant)
The quaternary ammonium salt value of the resin-type dispersant was determined by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into the equivalent amount of potassium hydroxide. The quaternary ammonium salt value of the resin-type dispersant shown below indicates the quaternary ammonium salt value of the nonvolatile content.

[Example 1]
(Production of compound (a))
In a reaction vessel, 7.1 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Thereafter, 8.7 parts of aluminum chloride and 10.0 parts of indigo were added, and the mixture was refluxed for 10 hours. After the reaction was completed, methanol was added and filtered to obtain a green powder. This was separated between dichloromethane and water, and the organic layer was concentrated to obtain 11.8 parts of compound (1).

[Compound (1)]

In a reaction vessel, 20.3 parts of compound (1), 13.5 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of N-methyl-2-pyrrolidone were mixed and stirred, and the temperature was raised. Afterwards, the mixture was stirred at 50°C for 2 hours. The reaction solution, which had been cooled to 30° C. while being stirred, was poured into 360 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 360 parts of methanol, then washed with 500 parts of water, and dried to obtain 14.0 parts of compound (a). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. FIG. 1 shows the infrared absorption spectrum of compound (a).

Compound (a)

[Example 2]
(Production of compound (b))
Compound (2) was prepared in the same manner as in the synthesis of compound (1), except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 9.2 parts of 2,6-dimethylaniline. I got 13.0 copies.

[Compound (2)]

20.3 parts of compound (1) used in the production of compound (a) was added to 22.0 parts of compound (2), and 13.5 parts of bis(2,4-pentanedionato)zinc(II) was added to zinc acetate. The same operation as in the production of compound (a) was performed except that the dihydrate was changed to 11.2 parts, to obtain 16.0 parts of compound (b). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. The infrared absorption spectrum of compound (b) is shown in FIG.

Compound (b)

[Example 3]
(Production of compound (c))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 10.1 parts of 5-aminoindole, and compound (3) was synthesized in 12.1 parts. I got 9 copies.

[Compound (3)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 22.6 parts of compound (3), and compound (c) was produced. 15.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (c)

[Example 4]
(Production of compound (d))
Compound (4) was prepared in the same manner as in the synthesis of compound (1), except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 12.4 parts of 3,5-dichloroaniline. 14.2 copies were obtained.

[Compound (4)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 24.4 parts of compound (4), and compound (d) was produced. 16.4 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (d)

[Example 5]
(Production of compound (e))
Compound (5) was prepared in the same manner as in the synthesis of compound (1), except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 9.8 parts of 3,4-difluoroaniline. I got 13.2 copies.

[Compound (5)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 22.4 parts of compound (5), and compound (e) was produced. 15.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (e)

[Example 6]
(Production of compound (f))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 13.1 parts of 4-bromoaniline, and compound (6) was synthesized in 14.1 parts of 4-bromoaniline. I got 3 copies.

[Compound (6)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 25.0 parts of compound (6), and compound (f) was produced. 16.6 copies of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (f)

[Example 7]
(Production of compound (g))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 8.2 parts of p-toluidine, and compound (7) was synthesized in 12.2 parts of p-toluidine. I got it.

[Compound (7)]

The same operation as in the production of compound (b) was carried out, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 21.1 parts of compound (7), and compound (g) was produced. 14.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (g)

[Example 8]
(Production of compound (h))
Compound (8) was prepared in the same manner as in the synthesis of compound (1), except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 10.6 parts of 4-(methylthio)aniline. I got 13.4 copies.

[Compound (8)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 23.0 parts of compound (8), and compound (h) was produced. 15.1 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (h)

[Example 9]
(Production of compound (i))
The same procedure as in the synthesis of compound (1) was performed, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 13.2 parts of sulfanilic acid, and 14.7 parts of compound (9) was obtained. Ta.

[Compound (9)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 25.0 parts of compound (9), and compound (i) 16.7 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (i)

[Example 10]
(Production of compound (j))
Compound (10 ) was obtained.

[Compound (10)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 22.1 parts of compound (10), and compound (j) was produced. 14.8 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (j)

[Example 11]
(Production of compound (k))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 9.4 parts of 3-methoxyaniline, and compound (11) was synthesized in 12. I got 6 copies.

[Compound (11)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 22.1 parts of compound (11), and compound (k) was produced. 15.0 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (k)

[Example 12]
(Production of compound (L))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 14.1 parts of 4-phenoxyaniline, and compound (12) was synthesized in 14.1 parts of 4-phenoxyaniline. I got 9 copies.

[Compound (12)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 25.8 parts of compound (12), and compound (L) was produced. 17.2 copies of this were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (L)

[Example 13]
(Production of compound (m))
The same procedure as in the synthesis of compound (1) was performed except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 12.5 parts of N,N-diethyl-1,4-phenylenediamine. , 14.1 parts of compound (13) were obtained.

[Compound (13)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 24.5 parts of compound (13), and compound (m) was produced. 16.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (m)

[Example 14]
(Manufacture of compound (n))
The same procedure as in the synthesis of compound (1) was carried out, except that 7.1 parts of aniline used in the synthesis of compound (1) was changed to 9.0 parts of 4-cyanoaniline, and compound (14) was synthesized in 12. I got 5 copies.

[Compound (14)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 21.8 parts of compound (14), and compound (n) was produced. 14.8 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

Compound (n)

[Example 15]
(Production of compound (o))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 16.0 parts of Bat Blue 35, and compound (15) was synthesized in 17.0 parts. I got 2 copies.

[Compound (15)]

The same operation as in the production of compound (b) was carried out, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 29.7 parts of compound (15), and compound (o) was produced. 19.5 parts of was obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (o)

[Example 16]
(Production of compound (p))
The same procedure as in the synthesis of compound (1) was carried out, except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 22.0 parts of Bat Blue 5, and compound (16) was synthesized with 22.0 parts of indigo. I got 8 copies.

[Compound (16)]

The same operation as in the production of compound (b) was performed, except that 22.0 parts of compound (2) used in the production of compound (b) was changed to 39.2 parts of compound (16), and compound (p) was produced. 25.3 copies were obtained. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (p)

[Example 17]
(Production of compound (q))

13.5 parts of bis(2,4-pentanedionato)zinc(II) used in the production of compound (a) was mixed with 13.1 parts of bis(2,4-pentanedionato)nickel(II) hydrate. 13.8 parts of compound (q) was obtained by carrying out the same operation as for producing compound (a), except that the procedure was changed to . As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (q)

[Example 18]
(Production of compound (r))

13.5 parts of bis(2,4-pentanedionato)zinc(II) used in the production of compound (a) was replaced with 14.8 parts of bis(2,4-pentanedionato)manganese(II) dihydrate. 13.7 parts of compound (r) was obtained by carrying out the same operation as in the production of compound (a), except that 1 part was changed. As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound (r)

[Example 19]
(Production of compound (s))
13.5 parts of bis(2,4-pentanedionato)zinc(II) used in the production of compound (a) was changed to 13.2 parts of bis(2,4-pentanedionato)cobalt(II). Except for this, the same operation as in the production of compound (a) was performed to obtain 13.7 parts of compound (s). As a result of mass spectrometry by TOF-MS, the obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.

compound(s)

[Comparative example 1]
(Synthesis of comparative compound (t))
A comparative compound (t) having the following structure was obtained according to JP-A No. 2013-87233.

compound (t)

<Method for manufacturing binder resin solution>
(Manufacture of binder resin 1 solution)
70.0 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device, and the temperature was raised to 80°C. After purging the inside of the reaction vessel with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a solution of acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin 1 solution was prepared by adding ether acetate.

(Manufacture of two binder resin solutions)
370 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80°C, and the inside of the flask was replaced with nitrogen. A mixture of 18 parts of cyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. . After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 part of hydroquinone were added to the container, and heated at 120°C. The reaction was continued for 6 hours, and the reaction was terminated when the acid value of the solid content reached 0.5, to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a solution of acrylic resin.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin 2 solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000.

(Manufacture of binder resin 3 solution)
207 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, and the temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from the dropping tube, add 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix (registered trademark) M110" manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, and 8.5 parts of 2-hydroxyethyl methacrylate. and 1.33 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of Karenz (registered trademark MOI), 0.08 parts of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content.Propylene glycol monomethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin 3 solution was prepared by adding ether acetate. The weight average molecular weight (Mw) was 18,000.

<Method for producing resin-type dispersant solution>

(Production of basic resin type dispersant 1 solution)
A reaction vessel equipped with a stirrer and a thermometer was charged with 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform, stirred at room temperature, and 50 parts of methacrylic acid chloride was added dropwise over 1 hour. After stirring at room temperature for 3 hours, after confirming that the reaction was complete by ¹ H-NMR, the reaction solution was washed successively with 300 parts of ion-exchanged water and 200 parts of saturated saline, and 20 g of magnesium sulfate was added to the organic layer. was added, stirred, and then filtered. The solvent in the obtained solution was distilled off using a rotary evaporator to obtain 58 parts of compound [B] represented by the following formula (5) as a pale yellow transparent liquid (yield: 85%). The obtained compound was identified by ¹ H-NMR.

Formula (5)

15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction tank equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated for 50 minutes while flowing nitrogen. The mixture was stirred at ℃ for 1 hour, and the inside of the system was purged with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were charged, and the temperature was raised to 110°C under a nitrogen stream to form the first block. Polymerization started. After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content.
Next, 25 parts of PGMAc and 30.3 parts of the above compound [B] as a second block monomer were added to the reaction tank, and the reaction was continued by stirring while maintaining the temperature at 110° C. and nitrogen atmosphere. Two hours after adding the compound [B] represented by the above formula (5), sample the polymerization solution and measure the solid content, and the polymerization conversion rate of the second block should be 98% or more in terms of non-volatile content. It was confirmed.
Further, 6.8 parts of benzyl chloride was added to this reactor, and the mixture was stirred for 3 hours while maintaining the temperature at 110° C. and nitrogen atmosphere, and then cooled.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by weight. In this way, basic resin type dispersant 1 with an amine value per solid content of 70 mgKOH/g, a quaternary ammonium salt value of 30 mgKOH/g, a weight average molecular weight (Mw) of 9,800, and a nonvolatile content of 40% by weight. A solution was obtained.

(Production of basic resin type dispersant 2 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. The system was stirred and replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were charged into this reactor, and the reaction was continued by stirring while maintaining the temperature at 110° C. and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content, and the reaction solution was cooled to room temperature. Polymerization was stopped by cooling.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, two basic resin type dispersant solutions were obtained, each having an amine value per nonvolatile content of 71.4 mgKOH/g, a weight average molecular weight of 9,900 (Mw), and a nonvolatile content of 40% by mass.

(Production of basic resin type dispersant 3 solution)
60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C for 1 hour while flowing nitrogen. The system was stirred and replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110° C. under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were introduced into the reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The mixture was stirred while the reaction was continued. Two hours after adding methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled to measure the nonvolatile content, and it was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of nonvolatile content. Polymerization was stopped by cooling to room temperature.
PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40% by mass. In this way, a basic resin type dispersant 3 solution having an amine value per nonvolatile content of 29.4 mgKOH/g, a weight average molecular weight of 9,800 (Mw), and a nonvolatile content of 40% by mass was obtained.

(Production of acidic resin type dispersant 4 solution)
10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer, and nitrogen gas was added. Replaced with. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by solid content measurement that 95% had reacted.
Added 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst, and reacted at 100°C for 7 hours. Ta. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was completed, and the solid content was diluted by adding propylene glycol monomethyl ether acetate so that the solid content was 40%. Four solutions of acidic resin type dispersants having a value of 70 mgKOH/g and a weight average molecular weight of 8,500 (Mw) were obtained.

(Manufacture of resin type dispersant 5 solution)
DISPER-BYK111 (manufactured by BYK Chemie Japan; acid value 129 mg KOH/g, solid content 95%) was diluted in the same manner as the resin-type dispersant 1 solution to prepare a resin-type dispersant 5 solution.

<Manufacture of near-infrared absorbing composition>
[Example 20]
(Near-infrared absorbing composition (D-1))
A mixture of the following composition was uniformly stirred and mixed, then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (a): 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts Based on the entire near-infrared absorbing composition (D-1) The water content was 1.1%, and the total amount of specific metal atoms was 180 ppm.

[Example 21]
(Near-infrared absorbing composition (D-2))
A mixture of the following composition was uniformly stirred and mixed, then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (a): 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 46.5 parts Ion exchange water: 1.0 parts Near-infrared absorbing composition ( D-2) The water content was 2.2% and the total amount of specific metal atoms was 185 ppm with respect to the whole.

[Example 22]
(Near-infrared absorbing composition (D-3))
A molecular sieve was added to the near-infrared absorbing composition (D-1), and the mixture was left to stand for 24 hours and filtered to obtain a near-infrared absorbing composition (D-3).
The moisture content of the entire near-infrared absorbing composition (D-3) was 0.1%, and the total amount of specific metal atoms was 177 ppm.

<Purification of compound (a) 1>
15.0 parts of compound (a) and 1000 parts of ion-exchanged water were placed in a beaker, heated and stirred at 60°C for 1 hour, filtered, washed with 2000 parts of ion-exchanged water, and dried.

<Purification of compound (a) 2>
15.0 parts of compound (a) and 1000 parts of methanol were placed in a beaker, heated and stirred at room temperature for 1 hour, filtered, washed with 500 parts of methanol and 2000 parts of ion-exchanged water, and dried.

<Purification of compound (a) 3>
In the synthesis of compound (a), the same operation as in Example 1 was performed, except that washing with 360 parts of methanol and then washing with 500 parts of water was changed to washing with 100 parts of water without washing with methanol. Ta.

[Example 23]
(Near-infrared absorbing composition (D-4))
Near-infrared absorbing composition (D-4) was prepared in the same manner as near-infrared absorbing composition (D-1) except that compound (a) was changed to the compound obtained in Purification 1 of compound (a). ) was prepared.
The moisture content of the entire near-infrared absorbing composition (D-4) was 1.0%, and the total amount of specific metal atoms was 100 ppm.

[Example 24]
(Near-infrared absorbing composition (D-5))
Near-infrared absorbing composition (D-5) was prepared in the same manner as near-infrared absorbing composition (D-1) except that compound (a) was changed to the compound obtained in Purification 2 of compound (a). ) was prepared.
The moisture content of the entire near-infrared absorbing composition (D-5) was 0.9%, and the total amount of specific metal atoms was 50 ppm.

[Example 25]
(Near-infrared absorbing composition (D-6))
Near-infrared absorbing composition (D-6) was prepared in the same manner as near-infrared absorbing composition (D-1) except that compound (a) was changed to the compound obtained in Purification 3 of compound (a). ) was prepared.
The moisture content of the entire near-infrared absorbing composition (D-6) was 1.2%, and the total amount of specific metal atoms was 1050 ppm.

[Examples 26 to 61, Comparative Example 2]
(Near-infrared absorbing compositions (D-7) to (D-42), (D-81))
Hereinafter, a near-infrared absorbing composition was prepared in the same manner as near-infrared absorbing composition (D-1) except that the composition and amount of the compound, resin-type dispersant solution, binder resin solution, and PGMAc were changed to those shown in Table 2. (D-7) to (D-42) and (D-81) were prepared.

[Example 62]
(Near-infrared absorbing composition (D-43))
A mixture of the following composition was uniformly stirred and mixed, then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a near-infrared absorbing composition. .
Compound (b): 7.0 parts Other near-infrared absorbing dye (X-1): 3.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47. 5th part

[Examples 63-99]
(Near-infrared absorbing compositions (D-44) to (D-80))
Hereinafter, near-infrared absorbing composition (D-43) was prepared in the same manner as near-infrared absorbing composition (D-43) except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 2. Absorbent compositions (D-44) to (D-80) were prepared. Note that (X-1) to (X-14) are other near-infrared absorbing dyes shown below.

Table 2 shows the compositions of the near-infrared absorbing compositions (D-1 to D-81). The water content of (D-7 to 81) is 0.1 to 2.0% by mass based on the total amount of the near-infrared absorbing composition, and the content of specific metal atoms is based on the total amount of the near-infrared absorbing composition. The amount was 1 to 1000 ppm by mass.

<Evaluation of near-infrared absorbing composition>
For the near-infrared absorbing compositions (D-1 to D-81) obtained in Examples and Comparative Examples, tests regarding dispersion stability, spectral properties, and resistance (light resistance, heat resistance) were conducted in the following manner. The results are shown in Table 3.

(Evaluation of dispersion stability)
The viscosity of the obtained near-infrared absorbing composition was measured and defined as the initial viscosity. Furthermore, an accelerated test was conducted at 40° C. for 7 days, and the accelerated viscosity over time was measured. As the rate of change due to acceleration, "viscosity accelerated over time/initial viscosity" was calculated, and the dispersion stability was evaluated using the following criteria.
◎ : Less than 1.05 ○ : 1.05 or more, less than 1.10 △ : 1.10 or more, less than 1.3 × : 1.3 or more

(Evaluation of spectral characteristics)
The obtained near-infrared absorbing composition (D) was spin coated onto a 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.0 μm, and dried at 60° C. for 5 minutes. , and heated at 230° C. for 20 minutes to produce a substrate. The absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
The average transmittance (T) of each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Table 3.

Spectral characteristics 1: 400nm to 550nm
○: 40% ≦ (T)
△: 25% ≦ (T) < 40%
×: (T) < 25%

Spectral characteristics 2: 700nm to 750nm
○: (T) ≦ 5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 3: 900nm to 1200nm
〇: 80% ≦ (T)
△: 60% ≦ (T) < 80%
×: (T) < 60%

(Light resistance test)
A test substrate was prepared in the same manner as in the spectral property evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and left for 24 hours. The absorbance of the near-infrared absorbing film at the maximum spectral absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated using the following criteria. Note that the residual rate was calculated using the following formula.
Survival rate = (absorbance after irradiation) ÷ (absorbance before irradiation) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more, less than 95% ×: Residual rate is less than 90%

(Heat resistance test)
A test substrate was prepared using the same procedure as for the spectral characteristic evaluation, and was additionally heated at 210° C. for 20 minutes as a heat resistance test. The absorbance at the maximum spectral absorption wavelength of the near-infrared absorbing film was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated using the following criteria. Note that the residual rate was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more, less than 95% ×: Residual rate is less than 90%

From the results in Table 3, the near-infrared absorbing composition containing the compound of the present invention has a high ability to cut near-infrared rays from 700 nm to 750 nm (spectral property 2), and has a high ability to cut near-infrared rays from 400 nm to 550 nm and from 900 nm onwards. It transmits external light (spectral properties 1 and 3), has good dispersion stability, and has excellent light resistance and heat resistance.

<Production of photosensitive near-infrared absorbing composition>
[Example 100]
(Photosensitive near-infrared absorbing composition (R-1))
After stirring and mixing the following mixture to make it homogeneous, 1. It was filtered through a 0 μm filter to obtain a photosensitive near-infrared absorbing composition (R-1).
Near-infrared absorbing composition (D-1): 50.0 parts Binder resin 2 solution: 7.5 parts Photopolymerization initiator ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiation Agent (“OXE-02” manufactured by BASF Japan): 1.5 parts PGMAc: 39.0 parts

[Examples 101 to 110 and Comparative Example 3]
(Photosensitive near-infrared absorbing compositions (R-2) to (R-12))
Hereinafter, a photosensitive near-infrared absorbing composition was prepared in the same manner as the photosensitive near-infrared absorbing composition (R-1) except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 4. Products (R-2) to (R-12) were obtained.

<Evaluation of photosensitive near-infrared absorbing composition>
For the photosensitive near-infrared absorbing compositions (R-1) to (R-12) obtained in Examples and Comparative Examples, tests regarding spectral properties and resistance (heat resistance, light resistance, etc.) were conducted in the following manner. Ta. The results are shown in Table 4.

(Evaluation of dispersion stability)
The viscosity of the obtained photosensitive near-infrared absorbing composition was measured and taken as the initial viscosity. Furthermore, an accelerated test was conducted at 40° C. for 7 days, and the accelerated viscosity over time was measured.
As the rate of change due to acceleration, accelerated aging viscosity/initial viscosity was calculated and evaluated using the following criteria.
◎ : Less than 1.05 ○ : 1.05 or more, less than 1.10 △ : 1.10 or more, less than 1.3 × : 1.3 or more

(spectral characteristic evaluation)
The obtained photosensitive near-infrared absorbing composition (R) was spin coated onto a 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.0 μm, and dried at 60° C. for 5 minutes. Afterwards, it was irradiated with 100 mJ/cm ² of ultraviolet rays using an ultra-high pressure mercury lamp, spray-developed with an alkaline developer consisting of a 0.2% by mass sodium carbonate aqueous solution, and then heated at 230°C for 20 minutes to produce a substrate. did. The absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
The average transmittance (T) in each range was calculated from the measured absorption spectrum, and evaluated using the same criteria as in the evaluation of the spectral characteristics of the near-infrared absorbing composition (D). The evaluation results are shown in Table 4.

Spectral characteristics 1: 400nm to 550nm
○: 40% ≦ (T)
△: 25% ≦ (T) < 40%
×: (T) < 25%

Spectral characteristics 2: 700nm to 750nm
○: (T) ≦ 5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 3: 900nm to 1200nm
〇: 80% ≦ (T)
△: 60% ≦ (T) < 80%
×: (T) < 60%

(Light resistance test)
A test substrate was prepared in the same manner as in the spectral property evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and left for 24 hours. The absorbance of the near-infrared absorbing film at the spectral maximum absorption wavelength was measured, the residual ratio to that before light irradiation was determined, and the light resistance was evaluated using the following criteria. Note that the residual rate was calculated using the following formula.
Survival rate = (absorbance after irradiation) ÷ (absorbance before irradiation) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more, less than 95% ×: Residual rate is less than 90%

(Heat resistance test)
A test substrate was prepared using the same procedure as for the spectral characteristic evaluation, and was additionally heated at 210° C. for 20 minutes as a heat resistance test. The absorbance at the maximum spectral absorption wavelength of the near-infrared absorbing film was measured, the residual ratio to that before the heat resistance test was determined, and the heat resistance was evaluated using the following criteria. Note that the residual rate was calculated using the following formula.
Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) x 100
◎: Residual rate is 95% or more ○: Residual rate is 90% or more, less than 95% ×: Residual rate is less than 90%

From the results in Table 4, the results of the photosensitive near-infrared absorbing composition (R) are similar to those of the near-infrared absorbing composition (D), and the near-infrared cutting ability is high from 700 nm to 750 nm (spectral characteristics 2 ), transmits visible light from 400 nm to 550 nm and near-infrared light from 900 nm onwards (spectral properties 1 and 3), has good dispersion stability, and has excellent light resistance and heat resistance.

<Manufacture of near-infrared cut filter>
[Examples 111 to 114]
(Near infrared absorption cut filters (F-1) to (F-4))
The photosensitive near-infrared absorbing composition (R-1) of the present invention was applied onto a 1.1 mm thick glass substrate using a spin coater, and heat-treated on a 100° C. hot plate for 1 minute as pre-baking.
Next, using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.), pattern exposure was performed through a photomask at an exposure dose of 1000 mJ/cm ² to form a near-infrared absorption cut filter of 100 μm square. .
After exposure, the uncured portion of the film was removed by shower development using a 0.2% by mass aqueous sodium carbonate solution as a developer and a developer pressure of 0.1 mPa to form a 400 μm x 400 μm pattern. Thereafter, post-baking was performed at 100°C for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after heat treatment was 1.0 μm.
Regarding the photosensitive near-infrared absorbing compositions (R-2) to (R-4), near-infrared cut filters (F-2) to (F- 4) was obtained.

<Evaluation of near-infrared cut filter>
Near-infrared cut filters (F-1) to (F-4) were tested for spectral properties and durability (heat resistance, light resistance) in the same manner as in the evaluation of photosensitive near-infrared absorbing compositions. The results are shown in Table 5.

From the results in Table 5, Examples 111 to 114 had excellent spectral characteristics. It has high transmittance in the visible light range from 400 nm to 550 nm (spectral property 1), excellent near-infrared absorption ability from 700 nm to 750 nm (spectral property 2), and transmits near-infrared light from 900 nm onwards (spectral property 3). ), and also has excellent light resistance and heat resistance. Therefore, it is suitable for a near-infrared cut filter.

<Production of near-infrared absorbing composition (visible light region absorbing composition) containing an organic dye having absorption in the wavelength range of 400 nm to 700 nm>

(Blue colored composition)
A mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a blue colored composition.
C. I. Pigment Blue PB15:6: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

(Purple colored composition)
A mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a purple colored composition.
C. I. Pigment Violet PV23: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

(yellow colored composition)
A mixture of the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill for 3 hours using zirconia beads with a diameter of 0.5 mm, and then filtered with a 0.5 μm filter to prepare a yellow colored composition.
C. I. Pigment Yellow PY139: 10.0 parts Resin type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[Example 115]
(Visible light region absorbing composition (P-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a visible light region absorbing composition (P-1).
Near-infrared absorbing composition (D-1): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin 1 solution: 7. 5 parts Photopolymerizable compound ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("OXE-02" manufactured by BASF Japan): 1.5 parts PGMAc

[Examples 116 to 119]
(Visible light region absorbing compositions (P-2) to (P-5))
Hereinafter, a visible light region absorbing composition (P-1) was prepared in the same manner as the visible light region absorbing composition (P-1) except that the near infrared absorbing composition was changed to the type of near infrared absorbing composition shown in Table 6. P-2) to (P-5) were obtained.

<Evaluation of visible light region absorbing composition>
The obtained visible light region absorbing composition was spin-coated onto a 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.0 μm, dried at 60°C for 5 minutes, and then heated at 230°C. was heated for 5 minutes to produce a substrate.
The function of the filter is, for example, whether it can transmit near-infrared rays and whether it can cut light rays in other wavelength ranges.
Below, the transmittance in the 900 to 1200 nm range and the absorption in the wavelength range of 400 to 750 nm were evaluated.

(400-750nm absorption)
The transmission spectrum of the obtained substrate in the wavelength range of 400 to 750 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
○: Transmittance is less than 2% in the entire range from 400 to 750 nm △: Transmittance is 2% or more in some region from 400 to 750 nm ×: Transmittance is 2% or more in the entire region from 400 to 750 nm

(900-1200nm transmission)
The transmittance of the obtained substrate from 900 nm to 1200 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
○: Transmittance is 80% or more in the entire range from 900 to 1200 nm △: Transmittance is 40% or more and less than 80% in some regions from 900 to 1200 nm ×: Less than 40% in some regions from 900 to 1200 nm

(Light resistance test)
The obtained substrate was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI) and left for 24 hours. At this time, the test was conducted using a broadband light of 300 to 800 nm with an irradiance of 47 mW/cm2. Thereafter, the transmission spectrum in the wavelength range of 400 to 750 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies).
○: Transmittance is less than 2% in the entire range from 400 to 750 nm △: Transmittance is 2% or more in some region from 400 to 750 nm ×: Transmittance is 2% or more in the entire region from 400 to 750 nm

(Heat resistance test)
The obtained substrate was additionally heated at 210° C. for 20 minutes as a heat resistance test. Thereafter, the transmission spectrum in the wavelength range of 400 to 750 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies).
○: Transmittance is less than 2% in the entire range from 400 to 750 nm △: Transmittance is 2% or more in some region from 400 to 750 nm ×: Transmittance is 2% or more in the entire region from 400 to 750 nm

From the results in Table 6, Examples 115 to 119 absorb light in the entire range of 400 to 750 nm and absorb light in the entire range of 900 to 1200 nm by containing both a near infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm. Can transmit near-infrared rays. Furthermore, it has excellent light resistance and heat resistance.

<Manufacture of near-infrared absorbing composition for molding>
(Thermoplastic resin (E))
(E-1) Polyester MA-2101M (polyester resin, manufactured by Unitika, crystalline resin, melting point 264°C)
(E-2) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265°C)
(E-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics, amorphous resin, glass transition temperature 145°C)
(E-4) Topas (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 78°C)
(E-5) Apel (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135°C)
(E-6) ULTEM (polyetherimide resin, Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217°C)

[Example 120]
(Manufacture of masterbatch)
1 part of compound (a) and 99 parts of thermoplastic resin (E-1) were charged into a twin screw extruder (manufactured by Japan Steel Works, Ltd.) with a screw diameter of 30 mm from the same supply port, and melted and kneaded at 300°C. After that, the mixture was cut into pellets using a pelletizer to prepare a masterbatch (M-1).

(Film molding)
5 parts of the obtained masterbatch (M-1) were mixed with 95 parts of the diluted thermoplastic resin (E-1), and heated to 300°C using a T-die molding machine (manufactured by Toyo Seiki). The mixture was melted and mixed to form a film (Q-1) with a thickness of 250 μm.

[Examples 121 to 150, Comparative Example 4]
In the same manner as in Example 120, films (Q-2) to (Q-32) with a thickness of 250 μm were molded using the materials listed in Table 7.

<Evaluation of near-infrared absorbing composition for molding>

(spectral characteristic evaluation)
The absorption spectrum of the obtained film in the wavelength range of 400 to 1200 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies). The average transmittance (T) of each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Table 8.

Spectral characteristics 1: 400nm to 550nm
○: 40% ≦ (T)
△: 25% ≦ (T) < 40%
×: (T) < 25%

Spectral characteristics 2: 700nm to 750nm
○: (T) ≦ 5%
△: 5% < (T) ≦ 10%
×: 10% < (T)

Spectral characteristics 3: 900nm to 1200nm
〇: 80% ≦ (T)
△: 60% ≦ (T) < 80%
×: (T) < 60%

(transparency)
The transparency of the obtained film was visually evaluated.
○: No turbidity observed at all.
△: Slight turbidity is observed.
×: Turbidity is clearly observed.

(light resistance)
A test film was prepared using the same procedure as for near-infrared absorption evaluation, placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI), and irradiated with broadband light from 300 to 800 nm at an irradiance of 47 mW/cm ² . , and left for 24 hours. Next, the test film was taken out, the absorbance at the maximum absorption wavelength of the test film was measured, the residual ratio to the absorbance before light irradiation was determined, and the light resistance was evaluated according to the following criteria. Note that the residual rate was calculated using the following formula.
Survival rate = (absorbance after irradiation) ÷ (absorbance before irradiation) x 100
○: Residual rate is 90% or more △: Residual rate is 85% or more and less than 90% ×: Residual rate is less than 85%,

From the results in Table 8, Examples 120 to 150 have high transmission in the visible light region from 400 nm to 550 nm (spectral property 1), and excellent near-infrared absorption ability from 700 nm to 750 nm (spectral property 2), and from 900 nm onwards. Transmits near-infrared light (spectral property 3), and has excellent transparency and light resistance.

<Production of visible light region absorbing composition for molding>
[Example 151]
(Manufacture of masterbatch)
1 part of compound (a), 1 part of Pigment Blue 15:3, 1 part of Pigment Yellow 147, 1 part of Solvent Red 52, and 96 parts of thermoplastic resin (E-1) were added through the same supply port with a screw diameter of 30 mm. The mixture was put into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.), melted and kneaded at 300°C, and then cut into pellets using a pelletizer to produce a masterbatch (MP-1).

(Film molding)
5 parts of the obtained masterbatch (MP-1) were mixed with 95 parts of the diluted thermoplastic resin (E-1), and heated to 300°C using a T-die molding machine (manufactured by Toyo Seiki). The mixture was melted and mixed to form a film (QP-1) with a thickness of 250 μm.

[Examples 152 to 168]
In the same manner as in Example 151, films (QP-2) to (QP-18) having a thickness of 250 μm were molded using the materials listed in Table 9.

The suitability of the near-infrared filter was evaluated for the obtained film. The function of the filter is, for example, whether it can transmit near-infrared rays and whether it can cut light rays in other wavelength ranges.
Below, the transmittance in the 900 to 1200 nm range and the absorption in the wavelength range of 400 to 750 nm were evaluated.

(400-750nm absorption)
The transmission spectrum of the obtained film in the wavelength range of 400 to 750 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
○: Transmittance is less than 2% in the entire range from 400 to 750 nm △: Transmittance is 2% or more in some region from 400 to 750 nm ×: Transmittance is 2% or more in the entire region from 400 to 750 nm

(900-1200nm transmission)
The transmittance of the obtained film was measured at 900 to 1200 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies).
○: Transmittance is 80% or more in the entire range from 900 to 1200 nm △: Transmittance is 40% or more and less than 80% in some regions from 900 to 1200 nm ×: Less than 40% in some regions from 900 to 1200 nm

(transparency)
The transparency of the obtained film was visually evaluated.
○: No turbidity observed at all.
△: Slight turbidity is observed.
×: Turbidity is clearly observed.

(light resistance)
The obtained film was placed in a light resistance tester ("SUNTEST CPS+" manufactured by TOYOSEIKI) and left for 24 hours. At this time, the test was conducted using a broadband light of 300 to 800 nm with an irradiance of 47 mW/cm2. Thereafter, the transmission spectrum in the wavelength range of 400 to 750 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies).
○: Transmittance is less than 2% in the entire range from 400 to 750 nm △: Transmittance is 2% or more in some region from 400 to 750 nm ×: Transmittance is 2% or more in the entire region from 400 to 750 nm

From the results in Table 10, Examples 151 to 168 absorb light in the entire range of 400 to 750 nm and absorb light in the entire range of 900 to 1200 nm by containing both a near infrared absorbing dye and a dye that absorbs visible light in the range of 400 to 700 nm. Can transmit near-infrared rays. Furthermore, it has excellent transparency and light resistance.

Claims (8)

A compound characterized by being represented by the following general formula (1).

General formula (1)


[In the formula, X ₁ to X ₁₂ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, and an aryl group that may have a substituent. Alkoxyl group, aryloxy group that may have a substituent, arylalkyl group that may have a substituent, cycloalkyl group that may have a substituent, Good alkylthio group, arylthio group that may have a substituent, amino group, alkylamino group that may have a substituent, arylamino group that may have a substituent, cyano group, halogen atom , nitro group, hydroxyl group, -SO ₃ H; -COOH; and monovalent to trivalent metal salts of these acidic groups; alkylammonium salts. Two adjacent groups among the groups represented by X ₁ to X ₁₂ may be connected to form a 5-membered ring or a 6-membered ring with the carbon atoms to which they are bonded.
M represents a metal atom. ] 2. The compound according to claim 1, wherein M is a divalent metal atom. A near-infrared absorbing composition comprising the compound according to claim 1 and a binder resin. The near-infrared absorbing composition contains a metal component containing a metal atom selected from Li, Na, K, Cs, Ca, Fe, and Zr, and in the entire near-infrared absorbing composition, the metal in the metal component The near-infrared absorbing composition according to claim 3, wherein the total amount of atoms is 1 to 1000 ppm by mass. The near-infrared absorbing composition according to claim 3 or 4, wherein the moisture content in the near-infrared absorbing composition is 0.1 to 2.0% by mass based on the entire near-infrared absorbing composition. Composition. The near-infrared absorbing composition according to claim 3 or 4, further comprising a polymerizable compound and/or a photopolymerization initiator. The near-infrared absorbing composition according to claim 3 or 4, further comprising an organic dye having absorption in the wavelength range of 400 nm to 700 nm. An optical filter comprising a coating formed from the near-infrared absorbing composition according to claim 3 or 4.